CN105431054A - Barrier layer capsules - Google Patents

Barrier layer capsules Download PDF

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Publication number
CN105431054A
CN105431054A CN201480039062.1A CN201480039062A CN105431054A CN 105431054 A CN105431054 A CN 105431054A CN 201480039062 A CN201480039062 A CN 201480039062A CN 105431054 A CN105431054 A CN 105431054A
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CN
China
Prior art keywords
active component
particulate
core
barrier layer
water
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Pending
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CN201480039062.1A
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Chinese (zh)
Inventor
A·L·多恩
M·查内
J·A·哈根
S·芬尼莫
N·尼寇洛瓦
D·谢格尔
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Givaudan SA
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Givaudan SA
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Publication of CN105431054A publication Critical patent/CN105431054A/en
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/70Fixation, conservation, or encapsulation of flavouring agents
    • A23L27/72Encapsulation
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23PSHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00Shaping or working of foodstuffs characterised by the products
    • A23P10/30Encapsulation of particles, e.g. foodstuff additives
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23PSHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00Shaping or working of foodstuffs characterised by the products
    • A23P10/30Encapsulation of particles, e.g. foodstuff additives
    • A23P10/35Encapsulation of particles, e.g. foodstuff additives with oils, lipids, monoglycerides or diglycerides
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs

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  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biophysics (AREA)
  • Nutrition Science (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Jellies, Jams, And Syrups (AREA)
  • Seasonings (AREA)
  • Medicinal Preparation (AREA)

Abstract

An active-containing microparticle is adapted to release the active in a desired end-use, comprising (a) an active-containing core active-containing core, optionally formed on an inner core, comprising a continuous hydrophilic medium in which at least one active is dissolved or is present as dispersed particles; (b) an active-free barrier layer, surrounding completely the core; and (c) surrounding the barrier layer, a layer of polymeric material having a solubility in water at 25 DEG C of 0.1% by weight maximum.

Description

Barrier layer capsule
The disclosure relates to for the delivery of particles of delayed release spices or other activating agents in Foods or drinks especially.
Packing has been widely used in be guaranteed active substance part or is protected completely, so that the time release expected.Such as, in the process of preparation consumer product compositions, packing can allow to add active component in the preparation of composition, processing or storage process, and be impossible in other situations, because preparation, processing or condition of storage can destroy the validity of active component, otherwise are exactly cause the validity of active component to reduce.The example of this situation can find in the application WO2004/089113 of PCT announcement, wherein capsule be used for preventing spices when storing oxidation (following description mainly refers to spices, the kind of the active component of particular importance, such as, but the scope of the disclosure is not limited to spices and is applicable to expect any active component of packing, the food of essence or perfume-free or consumable ingredient).
Although this kind of capsule is in fact for these objects, they are not all the time for more extreme condition, such as usual find in food-processing industry those.Especially Problems existing is the temperature (such as, in digestion process) being exposed to water and/or rising.This kind of condition may cause some or all spices losses, causes discharging in the processing of food, preparation or digestion process, or the spices of less desirable time release packing during life of product.Ideally, the spices of all packings should exist to send the flavor perception of expectation in finished product, but the condition that food usually runs in preparation and process of consumption may cause some composition losses of some or all spices or spices, or the different chemical composition of spices discharges with different rates.All these effects all can make flavour impression reduce in the quality of the time point of the expectation of life of product or intensity.
Make a large amount of trials overcoming these defects, but succeeded not yet completely.A kind of strategy is spices to be encapsulated in soluble in-core, and described core semipermeable polymeric nitride layer is covered.Semipermeable polymers is difficult to through the active component be delivered and is also difficult to through water.Ethyl cellulose is that drug delivery system is unified in perfume delivery system for the conventional polymer (such as WO2004/089113) of this object.This kind of capsule system is by osmotic pumps mechanism release of active ingredients, it is described to the drug delivery system (people such as such as M.Marucci, " Mechanisticmodelfordrugreleaseduringthelagphasefrompelle tscoatedwithasemi-permeablemembrane ", J.ControlledRelease, 2008, vol.127, pp.31-40).In the useful especially form of the one of this technology, active delivery particle comprises the external protection of core containing active component and at least one semipermeable polymers.Immerse water or be exposed to high relative humidity air in after, this kind of particle provides the lag time fully determined after such exposure, discharges the active material of most of packing subsequently with the speed of approximately constant in time.
But, send in the chemical substance of the different chemical structures with wide model have problems at this type systematic of use, such as find in spices, essence and food those.First, if different active components is encapsulated in capsule separately, they also have identical the Nomenclature Composition and Structure of Complexes, then the chemical property of active component may have major effect to the lag time of the capsule obtained and rate of release.This makes to be difficult to the release time-histories of prediction different activities agent in same food or essence articles for use.Secondly, the particle of the mixture of more than one activating agents of packing can be different from often kind of composition independent packing time the speed that discharges discharge different compositions, its mode is difficult to prediction.This two problems is the obstacle of research and development controlled release spices or essence goods.
Have been found that at present and can prepare active component release particles, its can for a long time and under the usual condition that this kind of particle is not tolerated retentive activity composition.Therefore, provide the particulate being applicable to discharge this active component in the final use expected containing active component, this particle comprises:
The a core containing active component that () is optionally formed on inner core, it comprises continuous hydrophilic media, and wherein at least one active component is dissolved in wherein or is discrete particles;
The barrier layer of (b) active substance, it surrounds described core completely; With
C () surrounds the polymer material layer of described barrier layer, described polymeric material has the solubility of 0.1% weight maximum at 25 DEG C in water;
Described barrier layer comprises the material of the material being selected from wax, fat and be suitable for the continuous hydrophilic media being used as described core, and it is solid under the condition of the final use expected.
Also be provided in the method providing the active component that can suitably discharge in the environment of consumer product compositions contact water and/or heating, described method comprises the active component adding particulate form in described consumer product compositions, and described particulate comprises:
The a core containing active component that () is optionally formed on inner core, it comprises continuous hydrophilic media, and wherein at least one active component is dissolved in wherein or is discrete particles;
The barrier layer of (b) active substance, it surrounds described core completely; With
C () surrounds the polymer material layer of described barrier layer, described polymeric material has the solubility of 0.1% weight maximum at 25 DEG C in water;
Described barrier layer comprises the material of the material being selected from wax, fat and be suitable for the continuous hydrophilic media being used as described core, and it remains solid when contacting water and/or heating.
The implication of so-called " can suitably discharge " refers to and can discharge in the time limit expected.The release time that the releasing properties of this expectation naturally depends on specific composition and expects, but the particulate of the disclosure can adapt to the release under all situations when the time of any desired.In each case, the mensuration of the particulate character be applicable to can be determined by normal experiment.
Core containing active component comprises the continuous media of wherein dissolving or dispersion of active ingredients (liquid or solid).More than one active components can be there are.Continuous media can be the material be applicable to arbitrarily, ready-to-serve hydrophilic (i.e. its swelling or dissolving in water) and can retentive activity composition.The example of the material be applicable to comprises the polysaccharide of long-chain and short chain polysaccharides class or replacement.Their instantiation comprises maltodextrin, monosaccharide, disaccharides, three carbohydrates or oligosaccharide kind, such as ribose, glucose, sucrose, fructose, sorbierite, sweet mellow wine, galactolipin, mannose or its mixture; Modified starch, such as butanedioic acid octene ester-functionalized starch; Emulsification natural gum, such as gum arabic and acacia gum, carrageenan or xanthans.Described medium can also be formed by the polysaccharide hydrogel such as pectin and alginates of protein hydrocolloid such as gelatin or replacement (for acid or metallic salt form) or be comprised them.
Continuous media containing active component can comprise complete core, or himself can be formed on inner core.This inner core can be solid or liquid.Such as, it can be arbitrary solid, Edible material, such as sugar, starch, cellulosic material and food acid.Or it can be liquid, and active component (identical or different with the active component in embracing layer) can be comprised.Such as, it can be the active component of 100%, or it can be scattered in or be dissolved in the active component in solvent or carrier liquid.Example comprises particle plant material, such as rice hulls.
Described active component can be that it exists and delayed release is the active component of any desired of expectation.Fragrance matter typically, the admixture of such as single fragrance component, or this constituents, and it can be liquid or solid form.But, the active component of other expectation arbitrarily can be used, such as pure aromatic substance.
What surround this layer containing active component is barrier layer.It can be formed by with the identical continuous media used in core, but not containing active component.The object of this layer is to postpone active component release, and its thickness is decided by the character of purposes and the delay time limit of expectation thus.But typically, the thickness of another layer this makes the weight fraction of its final particle be 3-80%, and condition is that it is at least 10 micron thickness.Concrete material for this layer is edible wax and fat.As long as they are edible, wax or fat can be used.Typical fat is di-glycerides and the triglyceride of naturally occurring glycerine.Wax can be natural wax or the wax of synthesis.Representative instance is hydrogenated triglyceride class, such as HPO, cotton seed oil, Canola Oil (canolaoil) or soybean oil; Or wax, such as beeswax, candelila wax, rice wax, Brazil wax or paraffin.
The major requirement of barrier layer is that it is solid under the final use condition expected.This final use will determine the material being used as barrier layer.Such as, if final use is involved in hot water or boiling water apply (such as, in soup), then selects barrier layer material, make this barrier layer keep solid under such conditions.Recognize that many potential barrier layer material do not have clear and definite fusing point, because they are pure chemical substance really, but softening in certain temperature range.In such cases, " solid " refers to that this material can soften, but can not flow at a certain temperature.Simple normal experiment can determine it in each case.
Final layer is the polymer material layer in water at 25 DEG C with the solubility of 0.1% weight maximum, and namely it is preferably insoluble in water under preparation and service condition.The example of the material be applicable to comprises ethyl cellulose, cellulose esters, cellulose ethers, zeins, polyvinyl acetate and lac.
Particle can be prepared by method known arbitrarily.When the particle without inner core, such as, can prepare the core containing active component in the following way: by making powder reunite, described powder is made by spraying dry in fluidized bed dryer; By make flavoring emulsion in fluidized bed dryer spraying dry to be accumulated as the large aggregation of 100-2000 micron magnitude range; By carrying out wet agglomeration to other spices powder in spray-dired powder or high shear mixing thing and extrude subsequently; Extrude by carrying out heat fusing to the dulcet matrix of tool; Or form the matrix granule based on hydrogel by the multiple emulsification in footpath, axial backmixing extruding, compacting or condensation technique.In often kind of these situations, the weight content of the spices in matrix is determined according to system composition and method therefor; This realizes easily through the use ordinary skill in the art.
Such as, this barrier layer can be coated with by the mode be applicable to arbitrarily as known in the art.Limiting examples comprises:
-by spraying as melt or being applied by solution, emulsion or the suspension be sprayed in fluid unit in water or nonaqueous solvents;
-apply as melt, emulsion or suspension in panning procedure;
-mix extrusion coated on core with the axial also axle that sprays of the form of the solution in water or nonaqueous solvents, emulsion or suspension.
Same procedure may be used for coating slightly solubility polymer material layer.The solution in water, one or more alcohols (typically ethanol or isopropyl alcohol) or its mixture can be it can be used as to be coated with, such as, to there is the ethanol optionally accounting for water weight 20% at the most).
Particulate mentioned above may be used for various consumer product compositions (composition namely absorbed in the oral cavity, for swallowing or spuing) widely, wherein expects active component delayed release.Therefore, also provide consumer product compositions, it comprises consumer product compositions matrix and the particulate containing active component as described above.
So-called " consumer product compositions matrix " refers to all that composition of the consumer product compositions of requisite expectation for composition, does not comprise particulate.They are the standard analysis (but being not limited to) used with art-recognized ratio: spices, colouring agent, surfactant, thickener and rheological agent, solvent, anticorrisive agent, sweetener, taste masking agents etc.
Described particulate added to some consumer product compositions with high water activity, then stored in the process of the time limit extended and may meet difficulty.Water activity a wit is well-known parameter in Food Science.It is in systems in which relative to the measured value of the water free energy of pure water, and is defined as and the vapour pressure of the vapour pressure of the water that food balances divided by pure water at identical temperature.The water activity of pure water is 1.Value in food is 0.97 to 0.2 in disintegrating machine in milk and fruit juice or following.But solid food can also have high a wvalue, such as raw meat (0.99) and salami (0.87).
High a win liquid environment such as canned soup, the result (several hours or longer, this depends on temperature and shearing condition) of long pot life limit is that particulate loses its inclusion most.Therefore, in order to optimum efficiency, use particulate with the form of the solid stored or semi-solid combination.In some cases, they can have high level, such as ice cream.In each case, the storage of particulate in the consumer goods and the adaptability of use can be determined by the experiment of simple non-creativeness.
The example of the consumer product compositions of particulate wherein can be used to comprise the Food & Drink of all kinds.The limiting examples of this kind of Food & Drink comprises: (guaranteeing that the example of consumer product compositions does not comprise those that do not provide applicable environment)
-dehydration and food for cooking, comprise boiling subsidiary products, such as: powder, particle, paste, concentrated liquid product, comprise the meat soup sample product of soup stock, meat soup and pressurization square, tablet or powder or particle form, they are sold (haveing nothing to do with technology) as finished product or the composition in product, flavouring and recipe mixture individually;
-meal solution product, such as: dehydration and cryodesiccated powder, comprise dried soup mix, dehydrated instant powder, dewatering prepares the powder of portion dish, ready-made dish, meals and single part of entree dehydration or environment goods, comprise pasta, vegetables, potato and rice dish, and freezing can these food type any of making of heat form again;
-meals decorative product, such as: dehydration or freezing flavouring, soak with romaine lettuce flavouring, salad-dressing, mayonnaise, dip thing (dips), breading, batter mix, barbecue mix comprise salad recipe mixture, as finished product or be no matter that composition in dehydration or freezing product is sold;
-beverage mix and concentrate, including, but not limited to alcohol and non-alcohol dry powdered beverage, all can the tea of rehydration form, coffee and cocoa;
-confectionary product, such as cake, biscuit, group, candy, chewing gum, ice cream, sherbet, pudding, jam, jelly and other flavouring, cereal and other breakfast foods, tinned fruit and fruit quelite etc.;
-soak with romaine lettuce flavouring and/or the frozen food of pasty state/roll bread crumb;
-refrigeration, freezing or can the milk of rehydration, cheese, yogurt and other dairy products.
Described particulate is in particular for food, and they must pass through the time limit adding heat fixation, such as, and not high a wthe soup of value, it tends to lose fragrance in heating process.Described particulate can make fragrance retain the long-time time limit, thus produces the final consumption product being full of fragrance.
Further describe the disclosure with reference to following non-limiting example, wherein, unless otherwise described, otherwise all numbers and ratio represent all by weight.
Embodiment 1: there is microcrystalline cellulose core and be coated with having and the particulate without barrier layer of ethyl cellulose containing acetophenone
Use microcrystalline cellulose spheres (Cellets tM700) inner core prepares particulate, at described microcrystalline cellulose spheres (Cellets tM700) be coated with acetophenone flavoring emulsion matrix on, this particulate has and does not have the barrier layer of MD6 starch, and it accounts for 9% of final particulate, and has final ethyl cellulose element coating, and described ethyl cellulose accounts for 10% of final particulate weight.
Core forms: by microcrystalline cellulose (Cellets tM700) spheric granules with 700-1000 micron magnitude range formed is used as core material.
The preparation of flavoring emulsion coating solution:
Following composition is used for 1kg gum arabic (GA) solution:
● gum arabic: 240g
● maltodextrin MD10:100g
● sorbierite: 60g
● water (running water): 600g
Whole powder is weighed into polybag with the above-mentioned consumption listed and fully mixes.Inclusion in bag is joined lentamente in water (being heated to 60 DEG C) under use top agitator stirs.After mixing, this solution is cooled to room temperature.Use high shear homogenizer (Ultra-TurraxT25 is with 24,000rpm) to mix 472.5g solution, and use this homogenizer at full speed to add acetophenone (63g) lentamente 1 minute.
Prepared by barrier layer solution: at 50 DEG C, prepare the solution of 25% maltodextrin MD6 and keep at such a temperature in coating process.
Final ethyl cellulose coating solution preparation: the ethyl cellulose solution in ethanol of preparation 10%.
Fluid bed arranges (GlattGPCG-3 spreader)
Use following condition:
Parameter Flavoring emulsion and barrier layer EC solution (in ethanol 10%EC)
Inlet air temperature DEG C 92 60
Product temperature DEG C 58-62 40-45
Nozzle exit pressure (bar) 3 3
Fluidization air (m3/h) 45-55 45-55
Before coating process starts, preheated fluidification bed is to avoid the cold spot in machine and to reach the product temperature of expectation fast.After preheating, machine is stopped, and 315g core is fed to fluidizing component.
Apply with flavoring emulsion. at once use the charging rate of 10g/ minute to start to apply emulsion (amounting to 535.5g) after again starting, described charging rate is enough low to avoid individual particle to reunite.The charging rate of GA emulsion adapts to this level lentamente, thus the product temperature of the expectation of enumerating in as above being shown (about 20g/ minute).
Coating barrier layer solution. by barrier layer solution (amounting to 252g) by the feed pipe identical with flavoring emulsion, to allow the feed rate (being also about 20g/min) maintaining the product temperature expected to join in fluid bed coater.Those are lacked to the particulate of barrier layer, skip this step.
Ethyl cellulose applies. and after emulsion coating or barrier layer coating, clean feed pipe and nozzle with water, and then use the ethanolic solution of ethyl cellulose (amounting to 700g) to start spraying.
In order to compare object, do not use some particulates of ethyl cellulose coating.
Measure from the flavor release rate of the particulate in water. use the USP2 device measuring being provided with fiber optics system for measuring the UV-visible absorbance as the function of time under controlled-shear conditions (HansonResearchSR8Plus with Cary50 spectrophotometer and CassiniMultiplexer) from the flavor release rate of particulate.Test under 30 DEG C and 150RPM oar rotating speed.
Result is as shown in the schematic diagram of Fig. 1." without coating " that curve marks discharges acetophenone in the core for never carrying out final EC applying step." EC " of curve mark is equivalent to apply the core that EC but uncoated interleave MD6 starch barrier layer." the EC+ barrier layer " of curve mark refers to the capsule with barrier layer+outer EC layer.Obviously, exist EC coating cause release to occur before significantly lag time and slowly rate of release.But, there is barrier layer and clearly be delayed release generation: discharge 2 times of acetophenone during the barrier layer of introducing around needed for 10% spices.
Embodiment 2: the particulate containing acetophenone and gaultherolin on fluid bed aggregation core, it is coated with 15% ethyl cellulose, has and does not have the barrier layer be made up of MD6 starch or high-melting-point palm oil fat (PO58).
By carrying out to having the spray-dired powder formed with the spices of system in embodiment 1 core that fluid bed agglomeration prepares these samples, except the acetophenone being about each 9% except final spices carrying capacity and gaultherolin (separately 63.5g being joined in flavoring emulsion).Coating scheme for ethylcellulose is in the same manner as in Example 1, but slightly different be PO58 layer, apply as follows.
Parameter PO58 coating
Inlet air temperature DEG C 50
Product temperature DEG C 45-48
Nozzle exit pressure (bar) 1
Fluidization air (m3/h) 35-45
Use PO58 barrier layer coated technique as follows.After spices coating, stop the method, and clean and dry feed pipe and nozzle cross-section.Then arranging in as above showing is used to apply PO58 coating (fixed rate of about 8g/ minute).PO58 is remained on 100 DEG C of temperature in coating process under; Use adds hot pursuit and feed pipe is heated to 100 DEG C.In addition, also nozzle air is heated to 100 DEG C, with the trend avoiding any PO58 to solidify in the feed line.
Coating EC coating after PO58 coating is carried out as described in example 1 above.Final PO58 weight in capsule is 10% weight.
Use method in the same manner as in Example 1 to measure the acetophenone rate of release of particulate, but temperature is 50 DEG C (also measure the release of gaultherolin, but as shown in its schematic diagram, close to equivalent acetophenone schematic diagram, ignore them).Period strong point refers to that the acetophenone without barrier layer discharges, and triangle refers to the release with MD6 barrier layer, and square refers to the release with PO58 barrier layer.
Can observe, there is MD6 barrier layer and be delayed spices release (correspondingly need to reach for about 20 minutes 10% spices release) occurs.It also suitably reduces the rate of release of two kinds of model flavor when the long period.There is PO58 barrier layer and clearly add lag time and the rate of release reducing spices.

Claims (11)

1. contain the particulate being applicable to discharge this active component in the final use expected of active component, comprise:
(a) optionally formed on inner core containing the core of active component, it comprises continuous hydrophilic media, wherein at least one active component be dissolved in wherein or as Granular composite in wherein;
The barrier layer of (b) active substance, it surrounds core matrix completely; With
C () surrounds the polymer material layer of described barrier layer, described polymeric material has the solubility of 0.1% weight maximum at 25 DEG C in water;
Described barrier layer comprises the material of the material being selected from wax, fat and be suitable for the continuous hydrophilic media being used as described core, and it is solid under the condition of the final use expected.
2. the particulate of claim 1, the continuous hydrophilic media wherein with the active component dissolving or disperse forms complete core.
3. the particulate of claim 1, wherein said core comprises inner core, and described inner core deposits the continuous hydrophilic media with the active component dissolved or disperse.
4. the particulate of claim 3, wherein said inner core is selected from sugar, starch, food acid and cellulosic material, particularly particle plant material.
5. the particulate of claim 1, wherein said core comprises inner core, and described inner core is liquid and optionally comprises active component, and this active component can be identical or different with the active component in continuous hydrophilic media.
6. the particulate of claim 1, wherein said active component is spices.
7. the particulate of claim 1, wherein said hydrophilic media is selected from the polysaccharide of long-chain and short chain polysaccharides class and replacement.
8. the particulate of claim 1, wherein said barrier layer is selected from edible wax and fat.
9. the particulate of claim 1, the polymeric material wherein having the solubility of 0.1% weight maximum at 25 DEG C in water is selected from ethyl cellulose, cellulose esters, cellulose ethers and lac.
10. consumer product compositions, comprises the particulate containing active component of consumer product compositions matrix and claim 1.
11. provide the method for the active component that can suitably discharge in the environment of consumer product compositions contact water and/or heating, and comprise the active component adding particulate form in described consumer product compositions, described particulate comprises:
The a core containing active component that () is optionally formed on inner core, it comprises continuous hydrophilic media, and wherein at least one active component is dissolved in wherein or is discrete particles;
The barrier layer of (b) active substance, it surrounds described core completely; With
C () surrounds the polymer material layer of described barrier layer, described polymeric material has the solubility of 0.1% weight maximum at 25 DEG C in water;
Described barrier layer comprises the material of the material being selected from wax, fat and be suitable for the continuous hydrophilic media being used as described core, and it remains solid when contacting water and/or heating.
CN201480039062.1A 2013-07-08 2014-07-08 Barrier layer capsules Pending CN105431054A (en)

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US201361843636P 2013-07-08 2013-07-08
US61/843,636 2013-07-08
PCT/EP2014/064515 WO2015004095A1 (en) 2013-07-08 2014-07-08 Barrier layer capsules

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CN107361392B (en) * 2017-07-26 2019-10-25 云南芯韵科技开发有限公司 A kind of three layers contain capsule with diuresis promoting function and preparation method thereof

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WO2015004095A1 (en) 2015-01-15
BR112015032594A2 (en) 2017-07-25
EP3027054A1 (en) 2016-06-08

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